Photographic element and process



u ow Aug. 31, 1943. v. B. SEASE EI'AL 2,328,034

PHOTOGRAPHIC ELEMENT AND PROCESS Filed" Dec. 14, 1940 1 Immqbi/e DyeIntermediate.

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Virgil 15.52352 UTi5W.MurI'a L| Rie-genrated. Cellulose and I PatentedAug. 1943 PHOTOGRAPHIC ELEMENT AND PROCESS Virgil B. Sease, NewBrunswick, and Otis Willard Murray, South River, N. J., assignors, bymesnc assignments, to E. I. du Pont de Nemours &

' Company, Wilmington ware , Del., a corporation of Application December14,1940, Serial No. 370,194

This invention relates to a novel process of color photography. Moreparticularly it relates to a novel process of producing color prints.Still more particularly it relates toa process for producing multicolorprints. ,Still'gmore particularly it relates to a process for producingdye images in films or plates which are tree from light'or radiationsensitive layers or strata, especially silversalt layers, or strata. Theinvention also relates to novel color.v elements for use inaforedescribed processes and tothe preparation of such elements.

This invention has for an of.a new process oi making'color prints. Afurther object is to provide a method of making color prints whichinvolves economical elements and processing baths; A still furtherobject is to provide a process for making multicolor prints whichinvolves a, few simple processing steps.

Another object is to provide a processfor making color prints whichrequires simple and economical equipment. Another object is to providenovel elements for making color prints which can be successfullyprocessed by-a few simple steps. A further object is to v provide novelelements in whichcolored images can be produced. Still other objects areto provide stable light insensitlve elements for making color prints andto make a general advance in the art.

The above objects may be accomplished by obiect the provision- 13Claims. (01. 95-2) three color separation negatives can be bleached in asimilar manner, then contacted with three separate color yieldingelements containing dye intermediates of the afore-described types whichare capable of forming three separate colored dye images, e. g. yellow,blue-green, and magenta. The color elements-are then superposed inregister, preferably to form a color print or color transparency. v

Various types of color elements may be made and used in accordance withthe teachings hereof. One practical type comprises a water impermeablebase member having superposed thereon a' water-permeable layer orstratum free from light sensitive salts or materials comprising a dyeintermediate capable of forming a quinoneimine dye including indophenol;indoaniline and indamine dyes, an azomethine dye or an azo dye by color'forming development, e.' g. with an arylenediamino developing'agent, ora hydrazine developing agent. The dye intermediate layer or strata maybe of two general types (1) composed of a dye intermediate or colorformer uniformly distributed or dispersed in a water-permeable bindingor supporting agent, and (2) composed of film forming materialcontaining within its the inventions which are hereinafter described andillustrated in the accompanying drawing.

In its broader aspects a color yielding element which comprises a waterpermeable stratum or layer containing -a dyestuff component capable offorming a quinoneimine, azomethine or "azo dye upon color formingdevelopment is contacted with a. separate element bearing a reduciblesilver salt or bleached silver image in the presence of a color formingdeveloping agent. The respective color elements and photographic elementare saturated with aqueous solutions prior to contact with each other.The color element is.

preferably saturated with an aqueous alkaline solution and thephotographic element bearing the silver salt image is preferablysaturated with an aqueous color forming developer solution prior tocontact development. The contact development is allowed to proceed untila colored or dye image is formed in the color element. The two elementsare then separated. The photographic element containing the silver saltimage may be contacted successively with a plurality of color imageelements after bleaching between each. contact development. Positivesprinted from structure dye forming nuclei, i. e. nuclei capable offorming a quinoneimine, azomethine or azo dye on color formingdevelopment. Gelatin, agar-agar, gum arabic, partially saponified poly-.merized vinyl acetate, gliadin, amino-cellulose salts, etc., formuseful binding agents.

The support of the above elements may be transparent and quite thin solong as they possess suilicient mechanical strength for processing andhandling, or they may be adhesively joined to a paper or transparentsupport of greater strength and/or thickness and/or to a thin membraneor support.

Another practical type comprises an element composed of water permeabletransparent ma-' terial having uniformly dispersed therein ordistributed therethrough, dye intermediates of types (1) or (2) as abovedescribed; Such elements should be of a thickness and possess a wetstrength suflicient to enable it to be processed, e. g. color developedin the above manner and washed and dried or transferred to a permanentsupport. Suitable materials include cellulose derivatives such asethers, e. g. ethyl, methyl and benzyl ethers, etc.; cellulose simpleand mixed 'esters, e. g. acetate, propionate, acetate-propionate; etherswith glycollic acid and its salts, etc., regenerated cellulose resins,e. g. hardened polyvinyl alcohol including partially hydrolyzed simpleor mixed polyvinyl esters of organic or inorganic acids such asthechloride, acetate, etc.,

a-hydrocarbon substituted acrylic acid esters, Y

.-etc., e. g. methyl methacrylate, various acetals of polyvinylalcoholderived from aldol, glyoxal and formaldehyde and containingsuitable plasticizers, etc.

Still another type of color element comprises a water-permeable colloidlayer or stratum having uniformly dispersed therein an immobile dyeintermediate of aforesaid type and an aromatic polyamine containing atleast one unsubstituted amino group. A small amount of an alkalinesulflte, for instance, sodium suliite in an amount equal to about 0.5%by weight of the developing agent, may be incorporated in the layer.This element may be processed in a similar manner but it is notnecessary to have an aromatic amino developing agent in the developersolution The color elements just described may contain more than onecolor yielding stratum on a single base in a single element. Thus, twodiiferent color yielding layers can be mounted on opposite sides of asingle transparent support composed of water impermeable material. Theimmobile dye components in the respective stratum should yield differentcolored dye images in order to obtain a multicolor picture. In analternative form;

two color elements may be placed on each side of a transparent basecomposed of water-permeable material of about 0.005 inch thickness.

In the accompanying drawing which will make the invention more easilyunderstood, similar reference numerals refer to similar parts throughoutthe several views. I

Fig. l is a cross-sectional view of a simple color element.

Fig. 2 is a cross-sectional view of a modified single color element.

Fig. 3 is a cross-sectional view of a further modified single colorelement.

Fig. 4 is a cross-sectional view of a further modified single colorelement.

Fig. 5 is a cross-sectional view of a stripping single color element.

Fig. 6 is a cross-sectional view of a photographic element bearing ableached silver halide image in contact with a stripping single colorelement during contact development.

Fig. 'l is a schematic cross-sectional view of a 3-color print made bycontact development of color elements of the type shown in Fig. 1.

The single color element of Fig. 1 which is useful for the production ofsingle color or composite prints, e. g. 3-color prints, comprises afilmcomposed of cold water-insoluble water-permeable material such as a.cellulose derivative such as lower alkyl ethers and highly estez'ifiedesters of cellulose, e. g. methyl cellulose, ethyl celluose, celluloseacetate, cellulose acetate propionate, regenerated cellulose, gelatin,agar-agar, and mixtures of these, etc., which contains an immobile dyeintermediate capable of forming a quinoneimine or azomethine dye with anaromaticamino developing agent uniformly distributed therethrough. Thethickness may vary in accordance with the properties of the materialused but in general should be suflicient to enable it to be processedand handled without rupture or disintegration. Various types of specificimmobile dye intermediates may be used. They may contain one or aplurality of groups which will enable dye coupling or color formingdevelopment to take place.

The dye intermediates or color formers may be 7 incorporated in thebinding agent before or after formation of the film I. The types whichare to be dispersed in gelatin or other similar colloid binding agentsmay be (1) substantive to 'the gelatin or binding agent, (2) soluble inaqueous alkaline liquids but fast to diifusion when present in emulsionlayers, (3) colloidal in nature so that they cannot be extracted bysimple extraction from the layer by aqueous treating liquids, (4) highmolecular weight so that migration through the cellular structure of,the binding agent is prevented, (5) highly insoluble, (8) film forming.

Substantivity can be strengthened by agents which have precipitatingaction, e. g. diphenyl guanidide, diphenylbiguanidide, etc.

The color element of Fig. 2 comprises a film 2 composed of film formingmaterial containing within its structure dye forming nuclei, 1. e.nuclei capable of forming a quinoneimine, azomethine or azo dye on colorcoupling, especially color forming development. Various polymeric andresinous color formers niay be used in this embodiment. The thicknessmay vary considerably depending on the-specific properties of the filmforming color former, but in general should be suiilcient to enable itto be processed and handled without rupture or disintegration.

According to Fig. 4 a gelatin dispersion of an immobile dye intermediateis coated on transparent film base 3 to form a thin layer 4. The

base may be composed of cellulose derivatives,

e. g.- cellulose nitrate, celluloseepropionateacetate, celluloseacetate, regenerated cellulose,

synthetic resins, e. g. polyvinyl acetals, esters, etc.,

acrylic acid esters, or superpolyamides, e. g. nylon. I

The stripping" type of color element of Fig. 5 represents an importantembodiment of the in vention. It comprises a transparent base 3 to whichis adhesively secured by layer I, a color element comprising atransparent membrane 6 which is preferably water permeable on which iscoated a layer 4 comprising ,a water permeable binding agent havinguniformly distributed therethroughan immobile dye intermediate of theabove-described types.

Various materials may be used for the mem- I branes which must be porousto aqueous fluids.

Suitable materials include collodion, synthetic resins, e. g. polyvinylesters such as partially hydrolyzed polymerized vinyl acetate; polyvinylacetals which are the condensation products of partially or completelyhydrolyzed polyvinyl acetate and an aldehyde such as formaldehyde,

r acetaldehyde or butyraldehyde, alkyd resins, i. e..

condensation products of polybasic acid compounds and polyhydroxylalcohols, e. g. from phthalic, adipic, succinic, maleic, fumaric, etc.acids and anhydrides with glycerol, ethylene glycol, diethylene glycol,ipentaerythritol, sorbitol, etc., nylon, i. e. film forming amidepolymers (see U. S. Patents 2,071,250, 2,071,253, 2,130,948 and2,141,169); etc. i

' The adhesive layer I can be composed of watersoluble orwater-swellable adhesives which have been used in prior art strippingfilms. A large. number of materials which are suitable for the adhesivestrata or layers are readily available and may be used in making thenovel stripping elements hereof. Water soluble, or alkali solublecellulose derivatives, e. g. methylcellulose, ethylcellulose, celluloseacetic acid'or cellulose glycollic acid and its water soluble salts,suchas alkali metal, ammonium and amine salts; water soluble starchderivatives, e. g. starch glycollic acid and its water soluble salts;water or alkali soluble resins, e. g. polyvinyl alcohol, polyvinyl vinylesters, e. g. formates, etc., alkyd resins, polyamides, water sensitivepolymeric amino-nitro gencontaining bodies, insoluble in water andammonium hydroxide, but soluble in aqueous acetic acid of concentrationsin the range of float away from the temporary support in de- Suitablespecific materials are deacetylated chitin, piperidylmethylzein,dicycloveloping baths.

hexylaminoethyl methacrylate, piperidy-l -N- ethyl methacrylate andmOrpholino-N-ethyl methacrylate.- Other materials of this type which maybe used include the deacetylated chitin which may be prepared accordingto Rigby U. S. Patent 2,040,879; the acid soluble reaction products ofproteins with carbonyl compounds such as'loweraliphatic aldehydes andketones and amines having less than nine carbon atoms in which theamino-nitrogen is joined to the allphatic carbon, foroexample, thosedisclosed in Meigs U. S. Patent 2,143,023, January 10, 1937; theaminocelluloses soluble in dilute acetic acid and containing anamino-nitrogen removed from the cellulose nucleus bya chain of atomscomprising at least one carbon atom, for example,

those described in Hardy U. S. Patent 2,136,296; cellulose amines whichare soluble in a stoichiometrical amount of 5% aqueous acetic acidcontaining directly attached to the cellulosic nucleus from 0.5 to 1.5amino-nitrogens per glucose unit, these amino-nitrogens being attachedto nucleus carbon atoms, for example, those in Haskins U. S.

Patent 2,136,299; reaction products of vinyl ketone polymers with aminocompounds, for example, those described in Balthis U. S. Patent2,122,707; the products obtained by treating resins having ketone groupswith anexcess of ammonia or the equivalent thereof and hydrogenating theresulting mixture catalytically at superatmospheric pressure andtemperature, such as those described in Greenewalt U. S. Patent2,063,158; polymeric amino alcohol esters of acrylic and substitutedacrylic acids, for example, those described in I-Iarmon'U. S. Patent2,138,762, November 29, 1938; and the polymeric amino alcoholmethacrylates described in Graves U. S. Patent 2,138,763; etc., singlyor in combination. These polymeric amino-nitrogen containing substancesare insoluble in" water and 5% aqueous ammonia but soluble in aqueousacetic acid of some' concentration within the range 25%. These solublein 2% acetic acid are preferred. These. polymeric-nitrogen containingsubstances may be divided in several groups as follows:

1) Those which may be termed cellulose derivatives. This includes,although not with strict accuracy, deacetylated chitin and thealkylamino and amino-alkylcelluloses above-identified.

(2) The second group consists in synthetic resins in the formation ofwhich ammonia in some instances and monomeric-amino-nitrogen.

containing bodies in other instances have been employed. This group isdistinct in that the highly polymeric molecules are built up wholly byartificial means. nature. In addition to the resinous polymeric aminoalcohol esters of acrylic acid or of its homologs substituted in thealpha position-by a hydrocarbon radical, there may be employed resinousreaction products of phenols, ,aldehydes and ammonia or primary orsecondary amines, for example, the reactionproduct of meta-cresol,formaldehyde and dimethylamine.

(3) The third group consists of protein derivatives containingsufficient amino-nitrogen to enablethem to meet the solubilityrequirements of the definition above given.

The color yielding elements above described may be further modified byincorporating with the .dye intermediates or color formers variouswetting agents or rewetting agents. Suitable agents of this type includethe water-soluble alkali metal, ammonium, substituted ammonium and aminesalts of alkyl and alkenyl sulfates having from 8 to 24. carbon atomsand of the corresponding alkyl sulfonic acids and of alkyl aromaticsulfonic acids, e. g. the naphthalene aromatic sulfonic acids having anaverage of 1 to 3 methyl, ethyl, isopropyl, or butyl groups and at leastone sulfonic acid group for each naphthalene molecule; the water solublesalts of the condensation products of formaldehyde with naphthalenesulfonic acids, etc. The use of such agents enables color formingdevelopment to take place in a more satisfactory manner and inhibitsair-bell and bubble formation. They also improve coating uniformity inmaking such ele- -ments.

-' These elements are not illustrated because their construction can bereadily visualized from a study of the existing figures.

The color elements hereof which contain color yielding layers oneach-side of a transparent .base may be used for the preparation ofmulticolor prints as set forth below or in accordance with the processesset forth in the copending application of O. W. Murray, filed December14, 1940, Serial No. 370,195.

The invention shall be further illustrated but is not intended to belimited by the following examples: a

EXAMPLE I PREPARATION or 3 -Cor.oa Pnmrs A. A cellulose nitrate filmbase 0.005" thick was coated with a thincellulose glycollateadhesivelayer on which was placed a thin cellulose nitrate stripping layer. Onthe stripping layer was coated a gelatin dispersion containing C. Athird color yielding element was made by substituting 1 gram ofdibenzoylacetbenzidide per 6.6 g. of gelatin.

They are not synthesized by From three color separation negatives wereprinted 3 positives on a transparent film base. The positives werebleached in an aqueous solution of potassium ferricyanide tosilverierrocyanide images, washed thoroughly, and soaked in 10% NazCOa.The stripping film units A, B and C each were soaked in Diethylp-phenylenediamine grams 10 misc; do 2 Metol i do 6 11:0 to cc 1000 Whenthese films are saturated with their respective solutions each issqueezed in intimate contact with the proper bleached color separationpositives, respectively, until a color image having the layers ofelements A and B, A and C,

or B and C on opposite sides of a single transparent base may besimilarly processed and a second single color element used therewith.

nxamm -n A. A cellulose acetate film base is coated to form a thinwater-soluble adhesive layer from a gelatine dispersion containing about2 parts of gelatin, 2 parts of dextrin and 96 parts of water. On thislayer was superposed a thin membrane or stripping layer composed ofcollcdion. On the stripping layer is coated a color yielding layer froma gelatin dispersion containing as a bluegreen color former about 1 gramof Z-hydroxy- 3-methyl benzaldehyde phthaldehydic acetal of polyvinylalcohol per 4 grams of gelatin.

B. A second color yielding unit .was prepared by substituting 4.5 partsof l-(m-octadecoylaminophenyl)-3-methyl-5-pyrazolone for the colorformer of unit A. I

C. A third color yielding unit was prepared by. substituting 3 parts ofacetoacetaminopheynlmorpholine for the color former of unit A.

Three color separation negatives of the type used for 3-colorphotography were used and processed to form three correspondingpositives on a film base. The positive silver images .were then bleachedto silver chloride images in a bath of the following composition:

CuSO4 gra'ms 100 NaCl do 100 H2804 conc cc 25 Water to liters 1 Each ofthe stripping units was soaked in a solution of the followingcomposition:

p-Amino-N-diethylaniline grams 2 Sodium sulfite, anhy do 1 Potassiumbromide do. 1 Water to liters 1 form a three color print.

EXAMPLE :1:

Film elements similar to A, B and c of Eb ample I were prepared bysubstituting for the respective color formers thereofn-octadecylonphenol, 4,4'-bis-(3"-methylpyrazolonyl-l") biphenyloxide,and diacetoacettolidine sulione.

From three color separation negatives were printed three positives on apositive film 'stock. The' positives after development fixing andwashing were bleached in a bath of the following approximatecomposition:

Potassium terricyanide grams 30 Ammonium hydroxide (cone) cc 5 Water todo 1000 washed, and soaked in 10% NazCOa. The respective bleachednegatives were then placed in contact and squeegeed with the appropriatecolor yielding elements A, B and C which hadbeen previously soaked in anenergetic developing solution of the following approximate composition:

p-Amino-N-diethylaniline grams 2 Ammonium hydroxide con cc 25 Sodiumsulfite, anhy grams 2 Water to liters-.. 1

After the dye images were formed in the color yielding element, theelements were separated, stripped and mounted in register on a whitepaper base thus forming an excellent -3-color print.

EXAIWPLEIV ,B. A similar element was made by substituting v sodiumstearoyl-J-acid for the blue-green dye intermediate of element A.

l .C. A similar element was made by substituting 1-phenyl-3-methyl-4paradimethylaminobenzol- E-pyrazolone for the dye intermediate 0!element A.

Three bleached positive color component im age records for 3-colorphotography are made after the maner set forth in Example I and soaked'with a dilute 5% solution of NaOH and pressed into contact with therespective color yielding layers of elements A and C which is previouslysoaked in an aqueous solution of the following formula:

\ Parts Monophenylhydrazine 2 2% aqueous sodium oleate 5 Sodium carbonat;- 2

layer are each stripped from the temporary supports and transferred to apermanent paper support to form a three-color print.

EXAMPLE v Film elements similar to'A, B and c of. Example I are made byincorporating in the gelatin dispersions in addition to the dyeintermediate about 2 parts of p-amino-N-diethyl-aniline.

,Three bleached positive color separation negatives are made in themanner set forth in ExampleI and soaked in an aqueous bath containing 2%of sodium oleyl sulphate, placed in. pressure contactwith the respectiveelements A, B

and C, which were previously soaked in an aqueous bath containing 30 cc.of hexamethalene-di amine-1,6 perliter of solution and squeegeed untilcolored images appear in the outer layers of the color yieldingelements.

EXAMPLE VI To a viscose dope consisting of water, cellulose xanthate andcaustic soda was added a dilute caustic soda solution ofp-hydroxybenzbic' acid positives on themetallic film base were thenformaldehyde resin. The resulting solution was flowed on glass plates,coagulated with ammonium sulfate and sodium sulfate-sulfuric acidsolutions and cleared with hot dilute sodium carbonate solution. Thefilms were then softened by treatment with glycerol solutions and driedunder tension. The resulting element when substituted for element A ofExample I gave similar results yielding a goodblue-green dye image. in

a regenerated cellulose film element.

EXAMPLE VII Four strippable dye-yielding elements were prepared asfollcws:

(A) Double-weight photographic paper stock was coated with a thinwater-soluble adhesive layer from a gelatine dispersion containing about2 parts of gelatine, 2 parts of dextrine and 96 parts of water. On thislayer was coated a thin stripping membrane composed of collodion. On thecollodion membrane was coated a coloryielding layer from a gelatinedispersion containing, as a blue-green color former, about 1 gram of2'-hydroxy-3 -methyl benzaldehyde phthalaldehydic acetal of polyvinylalcohol per 4 grams of gelatine.

(B) The second color yielding element was prepared by substituting 5.0parts of 1-.(m-octadecoyl-aminophenyl) -3-methyl-5-pyrazolone for thecolor former of unit A.

(C) The third color yielding unit was prepared by substituting 2 partsof diacetoacet-tolidine sulfone-o-benzaldehyde sulfonic acid dimer forthe color former of unit A.

- 407,830. A fourth positive was printed by combining the red and bluenegatives in register and with 10% soaked in a 10% sodium carbonatesolution. All

'of the dye-yielding stripping elements A, B, C,

and D were soaked in.a diethyl-p-phenylenediamine color developer asdescribed in Example I. The positives from the individual colorseparation negatives were rolled into intimate contact with the properbleached color separation positives until a color image was. formed in.the outer layers of each of such elements. More specifically, theblue-green dye-yielding element was squeegeed into contact with thebleached positive from the red separation negative; magenta yieldingelement was contact-developed with the positive from ,the greenseparation negative et cetera. The positive from the combined red andblue negative was contact-developed with the dye-yielding elementcontaining the neutral-gray dye-forming combination. When the colordevelopment was completed, the developed dye-yielding elements werestripped from their supports and transferred over to a permanent whitesupport such as barytes coated double-weight paper stock which waspreviously coated with a thin gelatine layer. The neutral gray key imagewas transferred first and the dye images were transferred in registeronto the base key image.

In this manner there is formed a four-color positive print withremarkably improved color quality with particularly faithful naturalcolor reproduction. By the use of the metallic film base for thepositives, it is possible to produce all four of the dye images withoutserious distortion as may occur in using positive emulsions coated onsupports which are water-sensitive thus causing lateral distortion inthe dye images and lack of registration. In place of the specific blackcolor formers set forth in this example, other neutral'color formers maybe substituted such as, N dodecyl-l; 2-hydroxy naphthoic acid-2- aminocarbazole, meta-dodecoylamino-phenylhydroxynaphthothiazole sulfonic acidmixed of 1- (m-stearoylaminophenyl) -3-' methyl-5-pyrazolone; 4-(a-hydroxynaphthoyl- 4'- (p-nitro-benzoylacetyl) -dichloro-benzidide.

Similar elements can be; made by substituting the following colorformers for the resin just mentioned:salicylaldehyde-o-sulfobenzaldehyde printing through these onto apositive emulsion coated on aluminum film base. I All four positiveprints were developed, fixed'and washed and then bleached to reduciblesilver ferrocyanide images as described in Example I. The bleachedacetal of polyvinyl alcohol, m-aminophenylmethyl pyrazoloneo-sulfobenzaldehyde-formaldehyde resin, and the 1-amino-8-naphtholsulfonic acid-ethylene-maleic anhydride interpolymer which whensubstituted as in Example I yielded blue-green, magneta and blue-greendye images, respectively.

In place of. the specific color yielding elements set forth in the aboveexamples may be substituted a wide variety ofother elements whichcontain different dye intermediates and coupling components, dispersingagents, wetting agents, adhesives, supports or base materials andmembranes as above-described. The resulting color yielding elementsmaybe 'used' with photographic elements containing bleached or reduciblesilver salt images in a similar manner to produce dye images. Thus,regenerated cellulose films ,containing immobile dye intermediates orelements which are essentially composed of film forming dyeintermediates can be soaked in developer. solutions or amine solutionsand squeegeed with photographic elements containing bleached silverimages in asimilar manner.

A plurality of color yielding units may be squeegee-developedinsuccession with the same ment should, in addition,

photographic element containing bleached or reducible silver saltimages. The element, however, must be bleached between each contactdevelopment operation. The photographic ele-- be dipped in alkalinesolutions between each contact development to insure a uniformity offinal prints. For in- .stance, 8 or good prints can be made from anoriginal negative or positive. The photographic elements can besuccessively bleached and contact-developed to a point of exhaustion ofthe eles-ient. I

The invention is not limited to the immobile dye intermediates or colorformers set forth in the examples, which are of the immobile type. Onthe contrary, they are merely illustrative of the operability of theinvention, but are not intended to limit its scope in any way. In placeof the specific color formers may be substituted a large number ofexceedingly diverse dye intermediates or color formers capable offorming indophenol, indoaniline, indamine, azomethine or azo dyes bycolor coupling development. The types which are to be dispersed ingelatin or other similar colloid binding agents are preferably immobileand may be (1) substantive to the gelatin or binding agent, (2) solublein aqueous alkaline liquids but fast to diifusion when present inemulsion layers, (3) colloidal in nature so that they cannot be removedby simple extraction from the layer, (4) of high molecular weight sothat migration through the cellular structure of the binding agent isprevented, (5) highly insoluble, (6) film forming. Substantivity can bestrengthened by agents which have precipitating action, e. g. diphenylguanidide, diphenylbiguanidide, etc.

The immobile dye intermediates or color formers in general contain twocomponents, (1) a color forming dye coupling component or nucleus and acomponent group or nucleus which increases the molecular weight so thatthey become immobile in water permeable colloid lay-, ers, or (2) groupsfor imparting substantive character (which may be of the same type asused in making dyestuffs substantive to cotton), or (3) groups orstructures which make itcolloidal in character.

Suitable dyestufi components for color-forming development and azocoupling processes hereof which fall within one or more of the abovetypes of immobile color formers include:

from polyvinyl alcohol or partially hydrolyzed polyvinyl esters andaromatic aldehydes which contain a phenolic hydroxyl, amino, alkyl-, cy-

cloalkyl-, or aryl-substituted amino group ineluding mixed groups ofthis type, which are further characterized in that they have a reactiveposition, but not necessarily unoccupied position, ortho or para to thementioned groups or the aromatic aldehydes having an active methylenegroup. The preparation of suitable compounds of this type is set forthin Dorough I; McQueen application, Serial No. 233,480, filed October 5,1938.

3. Condensation products of phenols and naphthols or hydroxv aromaticcarboxylic or sulfonic acids with difunctional resin forming reagentssuch as aldehydes and ketones, dimethylol derivatives of phenols, amidesand amines and equivalent compounds. The preparation of suitable colorformers of this type is described in Mc-' Queen application, Serial No.261,794, filed March 14, 1939.

4. Condensation products of amine-containing dye intermediates such asaminophenols, aminonaphthols, N-aminoallrylor aminoaryl-aminonaththols,amine containing active methylene compounds such as amino aroyloracetyl-acetanilides, amino-phenylmethylpyrazolones or any of thepreceding compounds containing solubilizing groups such as carbonyl orsulfonic, with polycarboxylic acids and their derivatives such as 1.Higher aliphatic and cycloaliphatic derivatives of dye intermediateswherein the aliphatic radical such as an alkyl, alkoxy or long chaincarboxylic acid acyl radicals contain a carbon chain of more than 8carbon atoms and preferably at least 12 carbon atoms, such compoundsincluding active methylene compounds such as aroylor acylacetanilides,phenylmethylpyrazolones, etc., higher aliphatic amides -of phenoliccompounds, and alphaand beta-naphthols which preferably contain somesolubilizing group such as carboxyl or sulf'onic, which arecharacterized in that they have a reactive position capable of en-'graphic color developers. The acetals are formed the anhydrides, esters,amides o2: halides. Such polymeric acids include the olefin-maleicanhydride interpolymers, polyacrylic .acids and interpolymers of estersof olefin dicarboxylic acids with vinyl esters, olefins and styrene asdescribed in U. S. Patent 1,945,307.

5. Immobile dye intermediates formed from N-mono and dialkylated or'aralkylated 1,5- and 1,8-aminonaphthols containing in a side chain agroup capable of further condensation such as amino, thio, carboxyl,formyl, etc., by condensing said compounds with a suitable highmolecular weight compound such as aliphatic acids or amines withmore-than 8 carbon atoms or polymeric materials such as polyvinylalcohol or polymeric acids or derivatives as listed above in paragraph4.

Suitable immobile dye intermediates of the above and other types whichare useful for color development and azo-coupling processes aredisclosed in U. 8. Patents 2,154,918, 2,166,181, 2,178,612, 2,179,228,2,179,238, 2,179,239, 2,179,244, 2,186,045, 2,186,719, 2,186,734,2,186,736, 2,186,849, 2,140,540, 2,186,735, 2,133,937, 2,200,924,2,213,986, etc., and may be substituted for the dye intermediates of theabove examples in accordance with the-teachings hereof.

Various types of developing solutions and agents which are capable offorming azcmethine or quinoneimine images may be substituted for thoseof the specific examples.

The preferred developing agents which may be used in the dye couplingdevelopment steps hereof are derivatives. of p-phenylenediamine andparticularly the'asymmetric dialkyl p-phenylenediamines of 1 to 4 carbonatoms, e. g. p-aminodimethylaniline, p-aminodiethylaniline,paminodibutylaniline, etc. Other developing agents which may be usedinclude p-phenylenediamine itself, p-methylaminoaniline,p-ethylaminoaniline, p-aminophenol, N,N diethyl-ophenylenediamine,chloro-p-phenylenediamine, 152,5 toluylenediamine, 2 amino .5 diethylaminotoluene, p-amino-N-phenylmorpholine, N-

p-aminophenylpiperidine, N-methyl-N-hydroxyethyl-p-phenylenediamine,N-butyl-N-hydroxyethyl-p-phenylenediamine, 2-amino-=5- (N-butyl-N-hydroxyethyD-amino toluene, p-y-dihydroxypropyl-p-phenylenediamine,etc. These aromat made of the hydrochloride, sulfates, acetates, etc.

Further examples of developing agents that can be used in this processare-heterocyclic compounds containing benzene nuclei such as1,2,3,4-tetrahydro-6-aminoquinoline,1,2,3,4-tetrahydro-G-amino-quinoxaline, etc (U. S. Patent 2,163,820);o-aminophenols and their substitution products; N-hydroxy-alkylp-phenylenediamines and di-N-hydroxyalkyl p-phenylenedh amines (U. S.Patent 2,108,243); halogenated paminophenols (British Patent, 467,087);pphenylenediamine derivatives containing solubilizing groups in thepositive radical connected to the N atom (U. S. Patent 2,163,166).

The developer solutions may further contain various other components ofdeveloper solutions. Thus, they may contain organic nitrogen bases freefrom negative groups and hydroxyl groups attached to carbon and havingan association exponent of 5.0 to 11.5 in an amount varying from about2.5 to 30 or more grams per liter of solution. Suitable agents of thistype include primary, secondary and tertiary alkyl monoand polyamines,having one to eight carbon atoms, heterocyclic amines, e. g. piperdineand its homologues, hydrocarbon substituted ammonium hydroxide, etc.Suitable bases are described in the following solutions which haveutility in processing the elements hereof. The

bases, however, may be used in water alone after the manner set forth inExample V.

Water to "liters- 1 Bath-F 2-amino-5-diethylamino-toluene grams 5Trimethy-l benzyl ammonium hydroxide 00.. 20 Sodium sulfite, anhy grams5 Water to liters 1 Bath-G 4:4 diaminodiphenylamine; grams 4Hexamethylenediamine cc 10 Sodium sulfite, anhy grams 2 Water to liters1 Bath-H 12'4-diaminonaphthalene grams 3 Dimethylcyclohexylamine cc 30Sodium sulfite, anhy "grams" 3. Water to liters 1 Bath-I4-diethylamino-l-naphthylamine lgrams 5 B dimethylaminoethylamine cc 20Sodium sulfite, anhy grams 5 Water to liters 1 Bath-J pAminodibutylaniline grams 3 Hexamethylenediamine solution in methanol)cc 20 Sodium sulfite, anhy grams 2 Water to liters 1 Bath-K I pAminodiethylaniline gram.s 3 Trimethyl-benzyl-ammonium h y d r 0 xi d eI cc 25 Sodium sulfite, anhy grams 3 Water to liters 1 chloronaphthylhydrazines, bromonaphthylhydrazines, p-diphenylhydrazines,p,p'-diphenyldihydrazines, p,p'-ditolyldihydrazines, a l p h anaphthylhydrazines, beta naphthylhydrazines which may be employed in theform of their salts,

e. g. hydrochloride, acetate, chloroacetate, sulfates, etc. Thehydrazines may be solubilized by means of long chain aliphaticcarboxylic acid salts, long chain aliphatic sulfonic acid salts as 3 setforth in Kirby application, Serial No. 299,762,

filed October 16, 1939, now United States Patent 2,240,929.

In place of the sodium carbonate solutions may be used potassiumcarbonate, potassium hydroxide, lithium hydroxide and other aqueousBath-A p-Amino N diethylaniline grams 2 Ammonium hydroxide, conc cc 25Sodium sulfite, anhy grams '2 Water to liters 1 Bath-B pAminodiethylanilina"; grams 2 Hexamethylenediamine (55% in methanol)Sodium sulfite, anhy grams 3 Water to liters 1 Bath-C I pAminodiethylaniline grams' 3 Ammonium hydroxide,pconc cc 30 Sodiumcarbonate, anhy "grams" 2' Water to liters v 1 Bath-D pAminodiethylaniline grams 3 B Dimethylaminoethylamine cc 20 Sodiumsulfite, anhy grams 3 'Water to--- L liters 1 Bath-E pAminodiethylaniline g rams 2 Piperidine cc 25 Sodium sulfite, anhy"grams" 2 solutions for soaking the bleached photographic elements. Theconcentrations may range somewhat depending on the pH of the particularagent, the bleaching agent used, the dye intermediate used and-theconcentration of the developing agent and amount of sulfite present.

In general concentrations of 2 to 15% are practical.

In making the above color yielding elements, the color formers may bemade into a paste with alkali and brought into solution with water oralcohol and then mixed with an aqueous dis- For example, the

onto a base having a substratum of the type suitable for anchoringsilver halide layers. The amount of dye intermediate may be the same asthat used'in prior art silver halide layers which contain immobile dyeintermediates. The dye intermediate may constitute from 20 to 100% ofthe weight of the binding agent, i. e. 1 to 5 parts of dye intermediateper 5 parts of binding agent. The same types of coating procedures usedfor silver halide emulsion layers have been found satisfactory. In thecase of film forming color formers, the aikaline aqueous or alcoholicsolutions may be cast in a similar manner.

'A number of different bleaching procedures can be used for theelements'which are used for contact development. Filmsor platescontaining a positive or negative silver image can be bleached toredevelopable silver salts, as for example, with potassium ferricyanide,copper chloride, or copper bromide in the presence of an oxidizing agentsuch as chromic acid, potassium ferricyanide in the presence of alkalicarbonate or ammonia, etc.

For the production of color prints and transparencies from strip orcontinuous film, e. g. colored cine prints or transparencies the dyeimages can be prepared in the same general manner as.

previously described. The color yielding element preferably should havethe same general dimensions as the photographic element for ease ofhandling and to promote economy. Intimate contact may be maintainedbetween the color element and the bleached element by running theelements in intimate contact after they have been suitably treated forcolor coupling through pressure rolls or down a belt until colorcoupling and the formation of dye images ha been completed.

The pressure rolls and belts are preferably provided with sprocketswhich fit into perforations in the color yielding elements andphotographic elements to insure accurate registration of images iftheyare mounted in registration with other color component records, e.g. from color separation negatives. of single color elementsthesprockets and perforations insureagainst slipping and the productionof fuzzy dye image records.

The color yielding units may be used for making single color'prints ofvarious types from photographic elements containing reducible silversalt images in an outer water permeable layer.

However, even in the case While the above description has beenrestricted for the most part to the formation of dye images innon-photographic layers by bringing a separate element containingreducible silver salt images into contact with the dye-yielding layer inthe presence of the constituents of a colorcoupling developer it is alsopossible to form such dye images in separate elements containingimagesother than silver salt images. For instance, one may employ the reducingaction of chromium oxides formed by exposing bichromated gelatin layers.For preparing such images, a film support is coated with a thin gelatinelayer, sensitized for example, by bathing in an alkaline bichromatesolution, dried and exposed under a negative to a printing lightcontaining some ultra-violet radiations. The e posed film element isthen soaked in alkali and pressed into contact with the color yieldingelement which has been saturated with a color coupling developingsolution. In fact, each of the above described procedures for imbibitionor con-- tact development can be used with the elements ontaining othertypes of developable images.

asaaoac A number of advantages are inherent in the processes andarticles of this invention. A major advantage resides in the fact' thata simple and economical process of making colored prints is provided. Afurther object resides in the fact that the invention eliminates a largenumber of the treating solutions and processing steps used in prior artprocesses. A further object resides in the fact that light insensitivecoloryielding elements which can be processed to color in the presenceof light are provided. A further advantage resides in the fact that thecolor yielding elements do not contain expensive silver salt layers. I

As many apparently widely different embodiments or this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that we do not limit ourselves to the specific embodimentsherein except as defined by the appended claims.

We claim: I

1. The process which comprises impregnating a photographic elementcontaining an image rec- 0rd in reducible silver salts in an outer layerthereof with an aqueous solution, impregnating a color yielding elementcontaining an immobile dye intermediate containing a component capableof forming a dye taken from the group consisting of quinoneimine andazomethine dyes in an outer layer thereof in a reducing solutioncontaining a color coupling developing agent and pressing said outerlayersinto contact until a dye image is formed in the latter element. I

2. The process which comprises impregnating a photographic elementcontaining an image record in reducible silver salts in an outer layerthereof with an alkaline aqueous solution, impregnating a color yieldingelement containing an immobile dye intermediate in an outer layer 5. Aprocess asset forth in claim 2 wherein said developing agent is anaromatic hydrazine.

6. The process which comprises soaking a photographic element containingan image record in reducible silver'salts in an outer layer thereof,soaking a color yielding element bearing a removable outer layercontaining an immobile color former in a stratum thereof in a reducingsolution containing a color coupling developing agent and pressing saidouter layers into contact until a dye image is formed in the latterelement.

'7. A process of making color prints which comprises printing positivesfrom color separation negatives, bleaching said positives, soaking saidpositives in dilute alkali, soaking color yielding elements containingimmobile dye intermediates which form dyes corresponding to the coloraspects of the separation negatives, in an outer.

layer thereof in a reducing solution containing a color couplingdeveloping agent and pressing said outer layers into contact until a dyeimage is formed in the latter element, separating said elements andmounting the elements containing dye images in register.

8. A process of making 3-color prints which comprises printing positivesfrom 3-color separation negatives, bleaching said positives, soakingsaid positives in dilute alkali; soaking color yielding elementscontaining immobile dye intermediates which form dyes corresponding tothe color aspects of the separation negatives, in an outer layer thereofin a reducing solution containing a color coupling developing agent andpressing said outer layers into contact until a dye image is formed inthe latter element, separating said elements and mounting the elementscontaining dye images in register.

9. The process which comprises impregnating a photographic elementcontaining an image record in reducible silver salts in an outer layerthereof with an aqueous alkaline solution, impregnating a color yieldingelement containing an immobile color former in an outer layer thereof inan aqueous reducing solution containing an aromatic primary amino colordeveloping agent, and pressing said impregnated layers into contactuntil a dye image is formed in the latter element.

10. The process which comprises printing color separation negatives onto separate light sensitive silver halide elements, developing andfixing said elements, bleaching the metallic silver images in saidelements. impregnating the elements in dilute aqueous alkaline solution,arate color yielding elements containing an immobile color former in awater permeable colloid outer layer thereof which forms a dyecomplementary in color to the color utilized in forming said negativesin an aqueous solution containing a primary amino color developingagent, pressing the outer layers of the respective photographic elementsand color yielding elements into contact until a dye image is formed inthe latter elements, and mounting the elements containing dye images inregister.

11. The process which comprises impregnating a photographic elementcontaining an image recimpregnating sep- 0rd in reducible silver saltsin an outer layer thereof with an aqueous solution, impregnating aseparate color yielding element containing a dyestuff intermediatecapable of color coupling development in an outer layer thereof with anaqueous solution and pressing the impregnated outer layers of saidelements into contact while subjecting them to the action of a colorcoupling developing agent until a dye image is formed in the coloryielding element.

12. The process which ing a photographic element which contains an imagerecord in reducible silver salts in an outer layer thereof with anaqueous solution, impregnating a separate color yielding elementcontaining an immobile dyestufi intermediate capable of color couplingdevelopment in an outer layer thereof with-an aqueous solution andpressing the impregnated outer layers of said elements into contactwhile subjecting them to the action of an aromatic primary amino 'colorcoupling developing agent until a dye image is formed in the coloryielding element.

13. The process which comprises impregnating a photographic elementcontaining an image record in reducible silver salts in an outer layerthereof with an alkaline aqueous solution, impregnating a color yieldingelement containing an immobile dye intermediate capable of forming a dyetaken from the group consisting of quinoneimine and azomethine dyes oncolor coucomprises impregnatpling development in an outer layer thereofin a reducing solution containing an aromatic primary amino colorcoupling developing agent and pressing said impregnated outer layersinto contact until a dye image is formed in the latterelement.

VIRGIL B. SEASE. OTIS W. MURRAY.

Patent No'. 2,528,051

CERTIFICATE OF CORRECTION.

August 51,. 191+ VIRGIL B. SEASE, ET AL.

It is hereby certified that error appears in the printed s pecificationof the above numbered patent requiring correction as follows Page )4,first column, line 14.6, for "acetoacetaminopheynl-f reed--acetoacetaminophenylline 66, before "images" insert --colorpage 5, firstcolumn, line 58, for "yeilding" reed "yieldingpage 6, second colunmsline 26, for "n'aththols" reao --naphthols-; page 7, first column,line 55, for "piperdine' and that read --piperidinein the Patent Office.

Signed and sealed this 26th day of October, A. D. .1925.

Henry Van Arsdale (Seal) Acting Commissioner of Patents.

the said Letters Patent should be read with this correction therein thatthe same may 'conform to the record of the case

